The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential
The human body contains ~10<sup>14</sup> cells—each of which is separated by a lipid bilayer, along with its organeller. Unsaturated fatty acids are located on the external layer and, as a result, are particularly exposed to harmful factors, including xenobiotics and ionising radiation....
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2025-01-01
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| author | Boleslaw T. Karwowski |
| author_facet | Boleslaw T. Karwowski |
| author_sort | Boleslaw T. Karwowski |
| collection | DOAJ |
| description | The human body contains ~10<sup>14</sup> cells—each of which is separated by a lipid bilayer, along with its organeller. Unsaturated fatty acids are located on the external layer and, as a result, are particularly exposed to harmful factors, including xenobiotics and ionising radiation. During this activity, lipid peroxidation products are generated, e.g., 4-hydroxy-2-nonenal (HNA), 4-oxo-2(<i>E</i>)-nonenal (ONE), and malondialdehyde (MDA). The mentioned aldehydes can react with cytosolic 2′-deoxynucleosides via Michael addition. In this paper, the following adducts have been taken into theoretical consideration: ε-dCyt, H-ε-dAde, ε-dCyt, H-ε-dAde, H-ε-dGua, <i>R</i>/<i>S</i>-OH-PdGua, <i>N</i>2,3-ε-dGua, M1-dGua, <i>N1</i>-ε-dGua, and HNE-dGua. The presence of the above molecules can alter a cell’s antioxidant pool. With this in mind, the adiabatic ionisation potential (AIP) and vertical ionisation potential (VIP), as well as the spin and charge distributions, are discussed. For this purpose, DFT studies were performed at the M06-2x/6-31++G** level of theory in the aqueous phase (both non-equilibrated (NE) and equilibrated (EQ) solvent–solute interaction modes), together with a Hirshfeld charge and spin distribution analysis. The obtained results indicate that the AIPs of all the investigated molecules fell within a range of 5.72 and 5.98 eV, which is consistent with the reference value of 7,8-dihydro-8-oxo-2′-deoxyguanosine (<sup>OXO</sup>dGua), 5.78 eV. <i>N</i>2,3-ε-dGua and M1-dGua were the only exceptions, whose VIP and AIP were noted as higher. The electronic properties analysis of 2′-deoxynucleoside adducts with lipid peroxidation products reveals their potential influence on the cells’ antioxidant pool, whereby they can affect the communication process between proteins, lipids, and nucleotides. |
| format | Article |
| id | doaj-art-601d1c236b9749e6a0563574981a2c6a |
| institution | Kabale University |
| issn | 2076-3417 |
| language | English |
| publishDate | 2025-01-01 |
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| spelling | doaj-art-601d1c236b9749e6a0563574981a2c6a2025-01-10T13:15:33ZengMDPI AGApplied Sciences2076-34172025-01-0115143710.3390/app15010437The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation PotentialBoleslaw T. Karwowski0DNA Damage Laboratory of the Food Science Department, Faculty of Pharmacy, Medical University of Lodz, ul. Muszynskiego 1, 90-151 Lodz, PolandThe human body contains ~10<sup>14</sup> cells—each of which is separated by a lipid bilayer, along with its organeller. Unsaturated fatty acids are located on the external layer and, as a result, are particularly exposed to harmful factors, including xenobiotics and ionising radiation. During this activity, lipid peroxidation products are generated, e.g., 4-hydroxy-2-nonenal (HNA), 4-oxo-2(<i>E</i>)-nonenal (ONE), and malondialdehyde (MDA). The mentioned aldehydes can react with cytosolic 2′-deoxynucleosides via Michael addition. In this paper, the following adducts have been taken into theoretical consideration: ε-dCyt, H-ε-dAde, ε-dCyt, H-ε-dAde, H-ε-dGua, <i>R</i>/<i>S</i>-OH-PdGua, <i>N</i>2,3-ε-dGua, M1-dGua, <i>N1</i>-ε-dGua, and HNE-dGua. The presence of the above molecules can alter a cell’s antioxidant pool. With this in mind, the adiabatic ionisation potential (AIP) and vertical ionisation potential (VIP), as well as the spin and charge distributions, are discussed. For this purpose, DFT studies were performed at the M06-2x/6-31++G** level of theory in the aqueous phase (both non-equilibrated (NE) and equilibrated (EQ) solvent–solute interaction modes), together with a Hirshfeld charge and spin distribution analysis. The obtained results indicate that the AIPs of all the investigated molecules fell within a range of 5.72 and 5.98 eV, which is consistent with the reference value of 7,8-dihydro-8-oxo-2′-deoxyguanosine (<sup>OXO</sup>dGua), 5.78 eV. <i>N</i>2,3-ε-dGua and M1-dGua were the only exceptions, whose VIP and AIP were noted as higher. The electronic properties analysis of 2′-deoxynucleoside adducts with lipid peroxidation products reveals their potential influence on the cells’ antioxidant pool, whereby they can affect the communication process between proteins, lipids, and nucleotides.https://www.mdpi.com/2076-3417/15/1/437polyunsaturated fatty acidslipid peroxidation products4-hydroxy-nonenalmalondialdehyde4-oxo-2-nonenal4-hyroxy-2-nonena |
| spellingShingle | Boleslaw T. Karwowski The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential Applied Sciences polyunsaturated fatty acids lipid peroxidation products 4-hydroxy-nonenal malondialdehyde 4-oxo-2-nonenal 4-hyroxy-2-nonena |
| title | The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential |
| title_full | The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential |
| title_fullStr | The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential |
| title_full_unstemmed | The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential |
| title_short | The Adducts Lipid Peroxidation Products with 2′-DeoxyNucleosides: A Theoretical Approach of Ionisation Potential |
| title_sort | adducts lipid peroxidation products with 2 deoxynucleosides a theoretical approach of ionisation potential |
| topic | polyunsaturated fatty acids lipid peroxidation products 4-hydroxy-nonenal malondialdehyde 4-oxo-2-nonenal 4-hyroxy-2-nonena |
| url | https://www.mdpi.com/2076-3417/15/1/437 |
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